Polyester resin and process for its production

ABSTRACT

A polyester resin characterized in that the content of the copolymerized components other than the terephthalic acid component and the ethylene glycol component, is not more than 4 mol % based on the total dicarboxylic acid component, and when polyester resin is formed into a molded product, the molded product has a specific absorbance.

TECHNICAL FIELD

The present application claims a benefit of Japanese Patent ApplicationNo. 2001-29135, and the content of this application will be referred toas a reference in the present specification.

The present invention relates to a polyester resin, whereby a moldedproduct excellent in a gas barrier property and also excellent in anultraviolet shielding property, a color tone, etc., and which isparticularly suitable for molding a bottle for e.g. a beverage requiredto have an aroma retention property, and further, to a polyester resin,whereby the acetaldehyde content in a molded product is reduced toeliminate an influence over the taste, aroma, etc. of the content, and aprocess for its production, whereby the polycondensability is improved.

BACKGROUND ART

Heretofore, a polyester resin such as a polyethylene terephthalate resinhas been widely used for packaging containers for various beverages,etc., since it is excellent in mechanical strength, chemical stability,gas barrier property, aroma-retention property, hygienics, etc., and isrelatively inexpensive and light in weight. Especially, as a containerfor a beverage which requires heat sterilization filling, for e.g. afruit juice beverage, a bottle having a high gas barrier property, etc.imparted by an application of stretch heat setting, has shown a rapidexpansion. Such a bottle is produced, for example, by injection moldinga bottomed tubular preform, reheating the preform to soften it, followedby stretch blow molding. At that time, the blow mold is heated to applyheat setting to the bottle, whereby crystals of molecular chains alignedby stretching are fixed to provide the high gas barrier property, etc.

However, with respect to the polyethylene terephthalate resin to be usedin such a field of beverage containers, in the case of a polyethyleneterephthalate resin produced by using an antimony compound as apolycondensation catalyst, which is most commonly used for bottles forwide range of purpose, copolymerizable components such as isophthalicacid, diethylene glycol, etc. other than the terephthalic acid componentand the ethylene glycol component, are copolymerized in an amount offrom about 3 to 10 mol % based on the total dicarboxylic acid componentin order to provide transparency, whereby the intended gas barrierproperty may not be obtained, whereby the aroma-retention property as abottle tends to decrease, and the aroma of the content is likely todecrease, or the ultraviolet shielding property tends to be poor,whereby the flavor component or the color tone of the content is likelyto deteriorate, and further, another problem is also worried such thatantimony remaining in the resin will elute from the container at a hightemperature and will transfer to the contained beverage althoughslightly. On the other hand, with a polyethylene terephthalate resinprepared by using a germanium compound as a polycondensation catalyst,which is commonly used for heat resistant bottles, copolymerizablecomponents other than the terephthalic acid component and the ethyleneglycol component, may be copolymerized in a relatively small amount at alevel of more than 2 to 5 mol % based on the total dicarboxylic acidcomponent, but the above-mentioned problem relating to a decrease of thearoma-retention property cannot still be solved, and the ultravioletshielding property is also inferior, and further, the germanium compoundis expensive, whereby an economical disadvantage cannot be avoided.Accordingly, it is strongly desired to have a substitutepolycondensation catalyst developed.

Further, many polyethylene terephthalate resins have been proposed whichare prepared by using titanium compounds as polycondensation catalysts,but they have had problems such that they lack in thermal stability, sothat the obtainable resins tend to have a yellowish color tone, or thechange in the color tone after being heated is substantial, and furtherhave problems such that acetaldehyde, a cyclic trimer, etc. are formedin a large amount as by-products during the polycondensation and themelt molding, and when used as bottles, they tend to deteriorate thetastes, aromas, etc. of the contained beverages. Whereas, e.g.JP-A-8-73581 discloses a process for producing a polyethyleneterephthalate resin which is colorless and excellent in transparency, byusing a titanium compound, a cobalt compound, and a limited amount ofcomplex-forming agent, such as phosphoric acid, phosphorous acid and/orphosphonic acid or its derivative. However, according to the studyconducted by the present inventors, it has been found that thepolyethylene terephthalate resin obtainable by this process is not onewhich is able to solve the above-mentioned problem such as a decrease inthe aroma-retention property and the problem such as deterioration ofthe taste, the aroma, etc. of the content.

Further, EP-A-1013692 discloses that production of acetaldehyde as aby-product during the polycondensation and the melt molding can besuppressed by using titanium and metal compounds, as polycondensationcatalysts, so that specific amounts of titanium atoms and metal atomssuch as magnesium, would be in a specific ratio. Further, inJP-A-2000-339919 filed by the present applicants, it is disclosed thatin the polycondensation in the presence of (1) a titanium compound, (2)a compound of at least one element selected from the group consisting ofmetal elements of Group 1A of the periodic table, elements of Group 2Aof the periodic table and manganese, and (3) a phosphorus compound, theorder of addition of the respective compounds (1), (2) and (3) is set tobe (3), then (2) and then (1), whereby by-products such as acetaldehyde,a cyclic trimer, etc., can be reduced. However, according to the studyby the present inventors, it has been found that these methods arecertainly effective to reduce by-products, but with the disclosedmethods, there is still a room for improvement with respect to the gasbarrier property, the ultraviolet shielding property or thepolycondensability.

The present invention has been made in view of the above-described priorart, and it is an object of the present invention to provide a polyesterresin, whereby a molded product excellent in the gas barrier propertyand also excellent in the ultraviolet shielding property, the colortone, etc., and which is particularly suitable for molding a bottle fore.g. a beverage required to have an aroma-retention property, andfurther, a polyester resin, whereby the acetaldehyde content as a moldedproduct is reduced to eliminate an influence over the taste, the aroma,etc. of the content, and a process for its production, whereby thepolycondensability is improved.

DISCLOSURE OF THE INVENTION

As its gist, the present invention provides a polyester resin producedby polycondensing a dicarboxylic acid component containing terephthalicacid or its ester-forming derivative as the main component, and a diolcomponent containing ethylene glycol as the main component in thepresence of (1) a compound of at least one member selected from thegroup consisting of titanium group elements in Group 4A of the periodictable, via an esterification reaction or an ester exchange reaction,characterized in that the content of copolymerized components other thanthe terephthalic acid component and the ethylene glycol component, isnot more than 4 mol % based on the total dicarboxylic acid component,and in a molded product with a thickness of 3.5 mm injection-molded at280° C., the difference between the absorbance at a wavelength of 395 nmand the absorbance at a wavelength of 800 nm is at least 0.08, and thedifference between the absorbance at a wavelength of 500 nm and theabsorbance at a wavelength of 800 nm is at most 0.05.

Further, as its gist, the present invention provides a process forproducing a polyester resin, which comprises polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component, and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table, (2) acompound of at least one element selected from the group consisting ofmetal elements of Group 1A of the periodic table, elements of Group 2Aof the periodic table, manganese, iron and cobalt, and (3) a phosphoruscompound, via an esterification reaction or an ester exchange reaction,characterized in that the amounts of the respective compounds (1), (2)and (3) are such amounts that their contents will be from 0.02 to 0.2mol as the total amount (T) of atoms of the compound (1), from 0.04 to0.6 mol as the total amount (M) of atoms of the compound (2) and from0.02 to 0.4 mol as the total amount (P) of atoms of the compound (3),per 1 ton of the polyester resin.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1(a): a plan view of a stepped molded plate for evaluation of thephysical properties, molded in Examples.

FIG. 1(b): a front view of the stepped molded plate for evaluation ofthe physical properties, molded in Examples.

BEST MODE FOR CARRYING OUT THE INVENTION

The polyester resin of the present invention is one produced bypolycondensing a dicarboxylic acid component containing terephthalicacid or its ester-forming derivative as the main component, and a diolcomponent containing ethylene glycol as the main component, via anesterification reaction or an ester exchange reaction, and is preferablya polycondensate of a dicarboxylic acid component in which theterephthalic acid component constitutes at least 96 mol %, morepreferably at least 99 mol %, of the total dicarboxylic acid component,with a diol component in which the ethylene glycol component constitutesat least 96 mol %, more preferably at least 97 mol %, of the total diolcomponent. If the proportion of the terephthalic acid component in thetotal dicarboxylic acid component, and the proportion of the ethyleneglycol component in the total diol component, are less than the aboveranges, the aligned crystallization of the molecular chains bystretching at the time of molding a bottle, etc., tends to beinadequate, whereby the mechanical strength, the gas barrier property,the heat resistance, etc., as a molded product such as a bottle, tend tobe inadequate.

And, in the polyester resin of the present invention, it is essentialthat the content of copolymerizable components other than theterephthalic acid component and the ethylene glycol component is notmore than 4 mol %, preferably not more than 3 mol %, further preferablynot more than 2 mol %. If the content of copolymerizable componentsexceeds the above range, it tends to be difficult to obtain a moldedproduct which is excellent in e.g. the aroma-retention property, etc.,and in which the acetaldehyde content is reduced.

Further, the ester-forming derivative of terephthalic acid may, forexample, be a C₁₋₄ alkyl ester, a halogenated product, etc. Further,dicarboxylic acid components other than terephthalic acid or itsester-forming derivative, may, for example, be an aromatic dicarboxylicacid such as phthalic acid, isophthalic acid, dibromoisophthalic acid,sodium sulfoisophthalate, phenylene dioxydicarboxylic acid,4,4′-diphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid,4,4′-diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid or2,6-naphthalene dicarboxylic acid, an alicyclic dicarboxylic acid suchas hexahydroterephthalic acid or hexahydroisophthalic acid, and analiphatic dicarboxylic acid such as succinic acid, glutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,undecadicarboxylic acid or dodecacarboxylic acid, as well as a C₁₋₄alkyl ester thereof, and a halogenated product thereof. Among them, inthe present invention, isophthalic acid or its ester-forming derivativeis preferred, and the proportion in the total dicarboxylic acidcomponent is preferably from 0.1 to 3 mol %. If isophthalic acid iswithin this range, the solid phase polycondensation rate is high, andreduction of the acetaldehyde content in a molded product of theobtainable resin tends to be facilitated.

Further, as the diol component other than ethylene glycol, diethyleneglycol formed as a by-product in the reaction system may be mentioned,and the proportion of such diethylene glycol in the total diol componentis preferably not more than 3 mol %, more preferably from 1 to 3 mol %,inclusive of one added as a copolymerizable component from outside thesystem. If diethylene glycol exceeds this range, a problem tends tooccur such that when the obtainable resin is formed into a moldedproduct, the gas barrier property decreases, or it tends to be difficultto reduce the acetaldehyde content. Further, other diol components may,for example, be an aliphatic diol such as trimethylene glycol,tetramethylene glycol, pentamethylene glycol, hexamethylene glycol,octamethylene glycol, decamethylene glycol, neopentyl glycol,2-ethyl-2-butyl-1,3-propane diol, polyethylene glycol orpolytetramethylene ether glycol, an alicyclic diol such as1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol,1,4-cyclohexanedimethylol or 2,5-norbornanedimethylol, and an aromaticdiol such as xylylene glycol, 4,4′-dihydroxybiphenyl,2,2-bis(4′-hydroxyphenyl)propane,2,2-bis(4′-β-hydroxyethoxyphenyl)propane, bis(4-hydroxyphenyl)sulfone orbis(4-β-hydroxyethoxyphenyl)sulfonic acid, as well as an ethylene oxideadduct or a propylene oxide adduct, of 2,2-bis(4′-hydroxyphenyl)propane.

Further, copolymerizable components may, for example, be ahydroxycarboxylic acid or an alkoxycarboxylic acid, such as glycolicacid, p-hydroxybenzoic acid or p-β-hydroxyethoxybenzoic acid, a singlefunctional component such as stearyl alcohol, heneycosanol, octacosanol,benzyl alcohol, stearic acid, behenic acid, benzoic acid, t-butylbenzoic acid or benzoylbenzoic acid, and a polyfunctional component withat least trifunctional, such as tricarbarylic acid, trimellitic acid,trimesic acid, pyromellitic acid, naphthalene tetracarboxylic acid,gallic acid, trimethylolethane, trimethylolpropane, glycerol,pentaerythritol or sugar ester.

The polyester resin of the present invention is such that in a moldedproduct with a thickness of 3.5 mm injection-molded at 280° C., thedifference between the absorbance at a wavelength of 395 nm and theabsorbance at a wavelength of 800 nm is at least 0.08, and thisdifference in absorbance is preferably at least 0.15, more preferably atleast 0.20. If this difference in absorbance is less than the aboverange, it tends to be difficult to obtain a molded product excellent inthe ultraviolet shielding property. Further, in a molded product havinga thickness of 3.5 mm injection-molded at 280° C., the differencebetween the absorbance at a wavelength of 500 nm and the absorbance at awavelength of 800 nm is at most 0.05, and this difference in absorbanceis preferably at most 0.04, more preferably at most 0.03. If thisdifference in absorbance is less than the above range, it tends to bedifficult to obtain a molded product excellent in the color tone. Here,the absorbance of a molded product is a value at each wavelength whenmeasured by means of an ultraviolet visible light absorption photometerwithin a wavelength range of from 300 to 800 nm at a scanning speed of127 nm/min.

Further, the polyester resin of the present invention is such that thetemperature-rising crystallization temperature (Tc) of the resin in themolded product after the injection molding at 280° C., is preferablyfrom 150 to 180° C., more preferably from 155 to 165° C., particularlypreferably from 157 to 164° C. This temperature-rising crystallizationtemperature (Tc) relates to the crystallization rate of the mouthstopper portion, etc. at the time of molding a bottle, and if thetemperature-rising crystallization temperature (Tc) is either less thanthe above range or more than the above range, the dimensional stabilityat the mouth stopper portion deteriorates as a bottle, and a problemsuch as leakage of a gas from the mouth stopper portion or deteriorationof the aroma-retention property, tends to result. Here, thetemperature-rising crystallization temperature (Tc) is one obtained bymeasuring the crystallization peak temperature observed in thetemperature rise when the temperature was raised from 20° C. to 285° C.at a rate of 20° C./min in a nitrogen stream by means of a differentialscanning calorimeter.

Further, the polyester resin of the present invention is such that theintrinsic viscosity ([η]) is preferably from 0.70 to 0.90 dl/g, morepreferably from 0.70 to 0.80 dl/g, as a value measured at 30° C. in asolution in a mixed solvent of phenol/tetrachloroethane (weight ratio:1/1). If the intrinsic viscosity ([η]) is less than the above range, themechanical strength tends to be inadequate as a molded product such as abottle. On the other hand, if it exceeds the above range, themoldability for a bottle or the like tends to deteriorate, and it tendsto be difficult to control production of acetaldehyde, etc. asby-products at the time of the melt molding. Further, as the color tone,the color coordinate value b of the Hunter's color difference formula inthe Lab color system as disclosed in Reference 1 in JIS Z8730, ispreferably not more than 4, more preferably from −5 to 2. If value bexceeds the above range, the color tone tends to be yellowish as amolded product such as a bottle. Further, the cyclic trimer content (CT)is preferably not more than 0.50 wt %, more preferably not more than0.40 wt %. If the cyclic trimer content (CT) exceeds the above range,contamination of the mold tends to occur during molding of a bottle,etc.

Further, the acetaldehyde content (AA₁) is preferably not more than 5.0ppm, more preferably not more than 3.0 ppm. Further, the acetaldehydecontent (AA₂) of the resin in a molded product after injection-molded at280° C., is preferably not more than 20 ppm, more preferably not morethan 18 ppm, particularly preferably not more than 15 ppm. If theacetaldehyde content (AA₁) and the acetaldehyde content (AA₂) exceed theabove ranges, it tends to be difficult to eliminate an influence overthe taste, the aroma, etc. of the content, as a molded product such asbottle. Further, the haze of a molded product with a thickness of 5 mmafter the injection molding at 280° C. is preferably not more than 10%,more preferably not more than 8%.

And, in the present invention, in order to bring the above-mentionedcontent of copolymerizable components, the intrinsic viscosity ([η]),color coordinate value b, the cyclic trimer content (CT), theacetaldehyde content (AA₁), as well as the absorbance of the moldedproduct after the injection molding at 280° C., the temperature-risingcrystallization temperature (Tc), the acetaldehyde content (AA₂), andthe haze, etc. within the above ranges, it is essential that thepolycondensation of the polyester resin is carried out in the presenceof (1) a compound of at least one member selected from the groupconsisting of titanium group elements in Group 4A of the periodic table.Accordingly, the polyester resin of the present invention contains (1) acompound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table.

Here, (1) the compound of a titanium group element of Group 4A of theperiodic table, i.e. titanium, zirconium or hafnium, may, for example,be an oxide, a hydroxide, an alkoxide, an acetate, a carbonate, aoxalate and a halide of such an element. Among compounds of suchelements, a titanium compound is preferred. Specifically, the titaniumcompound may, for example, be a titanium alkoxide such as tetra-n-propyltitanate, tetra-i-propyl titanate, tetra-n-butyl titanate, tetra-n-butyltitanate tetramer, tetra-t-butyl titanate, tetracyclohexyl titanate,tetraphenyl titanate or tetrabenzyl titanate, a titanium oxideobtainable by the hydrolysis of a titanium alkoxide, a titanium/siliconor zirconium double oxide obtainable by the hydrolysis of a mixture of atitanium alkoxide with a silicon alkoxide or a zirconium alkoxide,titanium acetate, titanium oxalate, titanium potassium oxalate, titaniumsodium oxalate, potassium titanate, sodium titanate, a titanicacid/aluminum hydroxide mixture, titanium chloride, a titaniumchloride/aluminum chloride mixture, titanium bromide, titanium fluoride,potassium hexafluorotitanate, cobalt hexafluorotitanate, manganesehexafluorotitanate, ammonium hexafluorotitanate, or titaniumacetylacetonate. Among them, a titanium alkoxide such as tetra-n-propyltitanate, tetra-i-propyl titanate or tetra-n-butyl titanate, titaniumoxalate or titanium potassium oxalate, is preferred, and tetra-n-butyltitanate is particularly preferred.

Further, with respect to the polycondensation, from the viewpoint of thepolycondensability, reduction of by-products such as acetaldehyde, acyclic trimer, etc. in the obtainable resin and the color tone, as wellas the absorbance of the molded product, the temperature-risingcrystallization temperature, etc., one polycondensed in the coexistenceof (2) a compound of at least one element selected from the groupconsisting of metal elements of Group 1A of the periodic table, elementsof Group 2A of the periodic table, manganese, iron and cobalt, and (3) aphosphorus compound, is preferred. Accordingly, the polyester resin ofthe present invention preferably contains (2) the compound of at leastone element selected from the group consisting of metal elements ofGroup 1A of the periodic table, elements of Group 2A of the periodictable, manganese, iron and cobalt, and (3) the phosphorus compound.

Here, (2) the compound of at least one element selected from the groupconsisting of metal elements of Group 1A of the periodic table, elementsof Group 2A of the periodic table, manganese, iron and cobalt, may, forexample, be an oxide, a hydroxide, an alkoxide, an acetate, a carbonate,an oxalate, a halide, etc. of lithium, sodium, potassium, magnesium,calcium, manganese, iron, cobalt, etc. Specifically, it may, forexample, be lithium acetate, sodium acetate, potassium acetate,magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesiumacetate, magnesium carbonate, calcium oxide, calcium hydroxide, calciumacetate, calcium carbonate, manganese oxide, manganese hydroxide,manganese acetate, ferric acetate, cobalt formate, cobalt acetate,cobalt oxalate, cobalt carbonate, cobalt bromide or cobaltacetylacetonate. Among them, a magnesium compound or a manganesecompound is preferred. Particularly preferred is a magnesium compound,and magnesium acetate is especially preferred.

Further, (3) the phosphorus compound may, specifically, be a pentavalentphosphorus compound, such as orthophosphoric acid, polyphosphoric acidor a phosphoric acid ester such as trimethyl phosphate, triethylphosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenylphosphate, tricresyl phosphate, tris(triethylene glycol) phosphate,methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate,butyl acid phosphate, monobutyl phosphate, dibutyl phosphate, dioctylphosphate or triethylene glycol acid phosphate, phosphorous acid,hypophosphorous acid, a phosphorous acid ester such as trimethylphosphite, diethyl phosphite, triethyl phosphite, trisdodecyl phosphite,trisnonyldecyl phosphite, ethyl diethyl phosphonoacetate or triphenylphosphite, or a trivalent phosphorus compound such as a metal salt oflithium, sodium, potassium, etc. Among them, a phosphoric acid ester asa pentavalent phosphorus compound is preferred. Particularly preferredis trimethyl phosphate or ethyl acid phosphate.

In the present invention, the respective amounts of (1) the abovecompound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table, (2) the abovecompound of at least one element selected from the group consisting ofmetal elements of Group 1A of the periodic table, elements of Group 2Aof the periodic table, manganese, iron and cobalt, and (3) the abovephosphorus compound, used at the time of polycondensation, and therespective contents in the resulting polyester resin, are preferablyfrom 0.002 to 1 mol, more preferably from 0.002 to 0.5 mol, as the totalamount (T) of atoms of the compound (1), preferably from 0.04 to 5 mol,more preferably from 0.04 to 3 mol, as the total amount (M) of atoms ofthe compound (2), and preferably from 0.02 to 4 mol, more preferablyfrom 0.02 to 2 mol, as the total amount (P) of atoms of the compound(3), per 1 ton of the polyester resin.

When the total amount (T) of atoms of the compound (1), the total amount(M) of atoms of the compound (2) and the total amount (P) of atoms ofthe compound (3) are within the above ranges, the ultraviolet shieldingproperties tend to be excellent. Further, particularly, in order toreduce the acetaldehyde content in the molded product and to improve thepolycondensability, the total amount (T) of atoms of the compound (1) ismore preferably from 0.02 to 0.2 mol, particularly preferably from 0.04to 0.15 mol, the total amount (M) of atoms of the compound (2) is morepreferably from 0.04 to 0.6 mol, particularly preferably from 0.05 to0.4 mol, most preferably from 0.1 to 0.3 mol, and the total amount (P)of atoms of the compound (3) is more preferably from 0.02 to 0.4 mol,particularly preferably from 0.1 to 0.0.3 mol, per 1 ton of thepolyester resin.

Further, once the amounts of the respective compounds i.e. (1) thecompound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table, (2) thecompound of at least one element selected from the group consisting ofmetal elements of Group 1A of the periodic table, elements of Group 2Aof the periodic table, manganese, iron and cobalt, and (3) thephosphorus compound, satisfy the molar amounts of the above ranges asthe total amount (T) of atoms of the compound (1), as the total amount(M) of atoms of the compound (2), and as the total amount (P) of atomsof the compound (3), it is preferred that the molar ratio [P/T] of thetotal amount (P) of atoms of the compound (3) to the total amount (T) ofatoms of the compound (1) is from 0.1 to 10, more preferably from 1 to7, particularly preferably from 2 to 5, and the molar ratio [M/T] of thetotal amount (M) of atoms of the compound (2) to the total amount (T) ofatoms of the compound (1) is from 0.1 to 10, more preferably from 0.5 to7, particularly preferably from 3 to 5. Further, for a polyester resinparticularly excellent in the ultraviolet shielding property, it ispreferred that the molar ratio [P/M] of the total amount (P) of atoms ofthe compound (3) to the total amount (M) of atoms of the compound (2),is more than 0 to 10, more preferably from 1 to 5, particularlypreferably from 2 to 4, and the molar ratio [P/(T+M)] of the totalamount (P) of atoms of the compound (3) to the sum of the total amount(T) of atoms of the compound (1) and the total amount (M) of atoms ofthe compound (2), is more than 0 to 10, more preferably from 0.5 to 5,particularly preferably from 1 to 3.

If the molar ratio [P/T] is less than the above range, the obtainableresin tends to be yellowish, and thus the color tone tends todeteriorate. On the other hand, if it exceeds the above range, the meltpolycondensability and the solid phase polycondensability, which will bedescribed hereinafter, tend to deteriorate simultaneously. Further, ifthe above molar ratio [M/T] is less than the above range, the meltpolycondensability and the solid phase polycondensability, which will bedescribed hereinafter, will deteriorate simultaneously, and it tends tobe difficult to reduce the acetaldehyde content in the molded product ofthe resulting resin. On the other hand, if it exceeds the above range,the solid phase polycondensability which will be described hereinafter,tends to deteriorate.

Further, in the present invention, during the polycondensation, metalcompounds other than the above-mentioned respective compounds, may bepresent within a range not to impair the effects of the presentinvention, and accordingly, such metal compounds may be contained in thepolyester resin of the present invention. In such a case, the metalcompounds may, for example, be compounds such as oxides, hydroxides,alkoxides, carbonates, phosphates, carboxylates or halides of aluminum,chromium, nickel, copper, zinc, germanium, molybdenum, silver, tin,lanthanum, cerium, tungsten, gold, etc. The above-mentioned respectivecompounds and other compounds are preferably ones soluble in water or analcohol such as ethylene glycol.

The polyester resin of the present invention is produced bypolycondensing a dicarboxylic acid component containing the aboveterephthalic acid or its ester-forming derivative as the main componentand a diol component containing ethylene glycol as the main component inthe presence of (1) the compound of at least one element selected fromthe group consisting of titanium group elements of Group 4A of theperiodic table, preferably in the coexistence of (2) the compound of atleast one element selected from the group consisting of metal elementsof Group 1A of the periodic table, elements of Group 2A of the periodictable, manganese, iron and cobalt, and (3) the phosphorus compound, viaan esterification reaction or an ester exchange reaction, but basicallyin accordance with a common process for producing a polyester resin.Namely, it is produced by introducing into a slurry preparation tank theabove dicarboxylic acid component containing the above terephthalic acidor its ester-forming derivative as the main component and the diolcomponent containing ethylene glycol as the main component together withoptional copolymerizable components, etc., followed by mixing withstirring to obtain a raw material slurry, subjecting it to anesterification reaction for from about 1 to 10 hours in anesterification reactor under atmospheric pressure or elevated pressureunder heating with stirring or to an ester exchange reaction in thepresence of an ester exchange catalyst, then transferring the obtainedpolyester low molecular weight product as the esterification reactionproduct or the ester exchange reaction product to a polycondensationtank, and melt polycondensing it in the presence of the above-mentionedcompounds under atmospheric pressure or gradually reduced pressure underheating with stirring for about 1 to 20 hours. These operations may becarried out by a continuous system or by a batch system.

At that time, preparation of the raw material slurry comprising thedicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component and the diol componentcontaining ethylene glycol as the main component, is carried outpreferably by adjusting the molar ratio of the total diol component tothe total dicarboxylic acid component to be within a range of from 1.0to 2.5, more preferably within a range of from 1.03 to 1.7.

Further, the esterification reaction is carried out by means of a singleesterification reactor or a multi-stage reaction apparatus having aplurality of esterification reactors connected in series, under refluxof ethylene glycol, while removing water formed by the reaction andexcess ethylene glycol out of the system. At that time, theesterification ratio (the proportion of the esterified by a reactionwith the diol component among the total carboxyl groups of the rawmaterial dicarboxylic acid component) of the polyester low molecularweight product as the esterification reaction product or the esterexchange reaction product, is preferably at least 95%. Further, thenumber average molecular weight of the low molecular weight product ispreferably from 500 to 5,000. Further, in the case of the ester exchangereaction, it is necessary to employ an ester exchange catalyst, wherebythe transparency of the resulting resin usually tends to be poor.Accordingly, in the present invention, the product is preferably oneproduced via the esterification reaction.

With respect to the reaction conditions in the esterification reaction,in the case of a single esterification reactor, the temperature isusually at a level of from 240 to 280° C., the relative pressure to theatmosphere is usually at a level of from 0 to 400 kPa (from 0 to 4kg/cm²G), and the reaction time is from about 1 to 10 hours withstirring. In the case of a plurality of esterification reactors, thereaction temperature in the esterification reactor for the first stageis usually from 240 to 270° C., preferably from 245 to 265° C., and therelative pressure to the atmospheric pressure is usually from 5 to 300kPa (from 0.05 to 3 kg/cm²G), preferably from 10 to 200 kPa (from 0.1 to2 kg/cm²G), and the reaction temperature in the final stage is usuallyfrom 250 to 280° C., preferably from 255 to 275° C., and the relativepressure to the atmospheric pressure is usually from 0 to 150 kPa (from0 to 1.5 kg/cm²G), preferably from 0 to 130 kPa (from 0 to 1.3 kg/cm²G).Further, the esterification ratio in each stage is preferably adjustedso that its increase will be equal.

Further, in the esterification reaction, it is possible to suppressproduction of diethylene glycol as a by-product from ethylene glycol, byadding a small amount of e.g. a tertiary amine such as triethylamine,tri-n-butylamine or benzyl dimethylamine, a quaternary ammoniumhydroxide such as tetraethylammonium hydroxide, tetra-n-butylammoniumhydroxide or trimethylbenzylammonium hydroxide, or a basic compound suchas lithium carbonate, sodium carbonate, potassium carbonate or sodiumacetate.

Further, the melt polycondensation is carried out under reducedpressure, while distilling off formed ethylene glycol out of the system,by means of a single melt polymerization tank, or a multi-stage reactionapparatus having a plurality of melt polycondensation tanks connected inseries, for example, an apparatus comprising a perfect mixing typereactor equipped with stirring vanes for the first stage and horizontalplug flow type reactors equipped with stirring vanes for the second andthird stages.

With respect to the reaction conditions in the melt polycondensation, inthe case of a single polycondensation tank, the temperature is usuallyfrom about 250 to 290° C., the pressure is gradually reduced from theatmospheric pressure, so that finally, the absolute pressure will beusually at a level of from 1.3 to 0.013 kPa (from 10 to 0.1 Torr), andthe reaction time is from about 1 to 20 hours with stirring. Whereas, inthe case of a plurality of polycondensation tanks, the reactiontemperature in the polycondensation tank for the first stage is usuallyfrom 250 to 290° C., preferably from 260 to 280° C. and the absolutepressure is usually from 65 to 1.3 kPa (from 500 to 10 Torr), preferablyfrom 26 to 2 kPa (from 200 to 15 Torr), and the reaction temperature inthe final stage is usually from 265 to 300° C., preferably from 270 to295° C., and the absolute pressure is usually from 1.3 to 0.013 kPa(from 10 to 0.1 Torr), preferably from 0.65 to 0.065 kPa (from 5 to 0.5Torr). The reaction conditions for an intermediate stage are selected tobe intermediate conditions thereof, and for example, in a three stagereaction apparatus, the reaction temperature in the second stage isusually from 265 to 295° C., preferably from 270 to 285° C., and theabsolute pressure is usually from 6.5 to 0.13 kPa (from 50 to 1 Torr),preferably from 4 to 0.26 kPa (from 30 to 2 Torr).

Further, at the time of polycondensation, timing for addition of (1) thecompound of at least one element selected from the group consisting oftitanium group elements of Group 4A of the periodic table, (2) thecompound of at least one element selected from the group consisting ofmetal elements of Group 1A of the periodic table, elements of Group 2Aof the periodic table, manganese, iron and cobalt, and (3) thephosphorus compound, to the reaction system, may be at any one of anoptional stage of a step of preparing a slurry of the starting materialterephthalic acid or its ester-forming derivative, ethylene glycol, andoptionally employed other dicarboxylic acid components, or a step of theesterification reaction or the ester exchange reaction, or in theinitial stage of the melt polycondensation step. However, the compounds(1) and (2) are added preferably in the step of the esterificationreaction or the ester exchange reaction, or in the stage oftransportation to the melt polycondensation step, and it is alsopreferred that they are added at a stage where the esterification ratioof the esterification reaction product or the ester exchange reactionproduct reaches at least 90%. Further, it is preferred that the compound(1) is added later than the compound (2). Further, it is preferred thatthe compound (3) is added at a stage where the esterification ratio ofthe esterification reaction product or the ester exchange reactionproduct is less than 90%.

With respect to the specific steps for addition of the respectivecompounds, it is preferred, for example, that the compound (1) is addedto the esterification reaction tank for the final stage in themulti-stage reaction apparatus or to the esterification reaction productor the ester exchange reaction product in the stage for transportationto the melt polycondensation step, and the compound (2) is added to theesterification reaction tank for the final stage in the multi-stagereaction apparatus. Further, the compound (3) is preferably added to theslurry preparation tank or the esterification reaction tank for thefirst stage, particularly preferably to the slurry preparation tank.Namely, in the present invention, it is preferred to set the order ofaddition of the respective compounds (1), (2) and (3) to the reactionsystem to be (3) then (2) and then (3).

By setting the timing of addition and the order of addition of therespective compounds (1), (2) and (3) to the reaction system asmentioned above, the thermal stability of the resin can be improved, andproduction of diethylene glycol as a by-product in the reaction systemwhich causes production of acetaldehyde, etc. as by-products during themelt molding, can be suppressed, and further, it is possible toeffectively obtain the effects for improving the melt polycondensabilityand the solid phase polycondensability.

Further, addition of the respective compounds (1), (2) and (3) to thereaction system at the time of the polycondensation, is preferablycarried out in the form of a solution in e.g. water or an alcohol suchas ethylene glycol. In an ethylene glycol solution in a case where atitanium compound is used as the compound (1), it is preferred to adjustthe concentration of titanium atoms to be from 0.01 to 0.3 wt % and thewater concentration to be from 0.1 to 1 wt %, from the viewpoint of thedispersibility of the titanium compound in the reaction system and theimprovement of the melt polycondensability and the solid phasepolycondensability thereby obtainable.

Further, the reaction time for the melt polycondensation is usuallypreferably at most 3.5 hours. If the reaction time exceeds it, it tendsto be difficult to reduce the aldehyde content in the resulting resinand the amount of acetaldehyde by-product during the melt molding.

The polyester resin obtainable by the above melt polycondensation issuch that the intrinsic viscosity ([η₁]) is preferably from 0.35 to 0.75dl/g, more preferably from 0.50 to 0.60 dl/g, as a value measured at 30°C. in a solution in a mixed solvent of phenol/tetrachloroethane (weightratio: 1/1). If the intrinsic viscosity ([η₁]) is less than the aboverange, the withdrawing property from the polycondensation tank, whichwill be described hereinafter, tends to be poor. On the other hand, ifit exceeds the above range, it tends to be difficult to reduce theacetaldehyde content in the resulting resin. Further, the meltpolycondensation velocity (V₁) as a value obtained by dividing theabove-mentioned intrinsic viscosity ([η₁]) of the resulting polyesterresin by the above-mentioned reaction time, is preferably at least 0.15dl/g/hr.

Further, the resin obtained by the melt polycondensation is usuallywithdrawn in the form of a strand from a discharge outlet provided atthe bottom of the polycondensation tank and, while being cooled by wateror after being cooled by water, cut by a cutter into particles such aspellets or chips. Further, such particles after the meltpolycondensation, are usually heated at a temperature of from about 60to 180° C. in an atmosphere of an inert gas such as nitrogen, carbondioxide or argon, or in a steam atmosphere, or in a steam-containinginert gas atmosphere, to crystallize the surface of the resin particlesand then subjected to solid phase polycondensation by heat treatment ata low temperature of from immediately below the adhesive temperature ofthe resin to 80° C. in an inert gas atmosphere or/and under a reducedpressure of from 1.3 to 0.013 kPa (from 10 to 0.1 Torr), usually for aperiod of at most 50 hours, while letting the particles flow not to fuseone another. By this solid phase polycondensation, it is possible tofurther increase the polymerization degree and to reduce by-productssuch as acetaldehyde, a cyclic trimer, etc.

The polyester resin obtainable by the above solid phase polycondensationis such that the intrinsic viscosity ([η₂]) is preferably from 0.70 to0.90 dl/g, more preferably from 0.70 to 0.80 dl/g, as a value measuredat 30° C. in a solution in a mixed solvent of phenol/tetrachloroethane(weight ratio: 1/1). Further, the solid phase polycondensation velocity(V₂) as a value obtained by dividing the difference ([η₂]−[η₁]) betweenthe above intrinsic viscosity ([η₂]) of the obtainable solid phasepolycondensation resin and the intrinsic viscosity ([η₁]) of theabove-mentioned melt polycondensation resin, by the above-mentionedreaction time, is preferably from 0.008 to 0.015 dl/g/hr. Further, theratio (V₂/V₁) of this solid phase polycondensation velocity to theabove-mentioned melt polycondensation velocity is preferably within arange of from 0.04 to 0.07, more preferably within a range of from 0.05to 0.07.

Further, for the purpose of improving the thermal stability, reductionof by-products such as acetaldehyde, a cyclic trimer, etc. during themolding, etc., the resin obtained by the above melt polycondensation orthe solid phase polycondensation may usually be subjected to watertreatment of dipping it in warm water of at least 40° C. for at least 10minutes, or steam treatment of contacting it with steam or asteam-containing gas of at least 60° C. for at least 30 minutes, ortreatment with an organic solvent, an acidic aqueous solution of e.g.various mineral acids, organic acids or phosphoric acids, or treatmentby an alkaline aqueous solution or an organic solvent solution, of aGroup 1A metal, a Group 2A metal or an amine.

Further, the polyester resin of the present invention may contain acrystalline thermoplastic resin different from the polyester resin in acontent of from 0.0001 to 1,000 ppm, preferably from 0.0005 to 100 ppm,more preferably from 0.001 to 10 ppm, as the case requires, to adjustthe temperature-rising crystallization temperature (Tc) of the resin inthe above-mentioned molded product after injection molding to theabove-mentioned range. As such a crystalline thermoplastic resin, apolyolefin resin or a polyamide resin may be mentioned as a typicalexample.

The polyolefin resin may, for example, be a homopolymer of an α-olefinhaving from about 2 to 8 carbon atoms, such as ethylene, propylene orbutene-1, or a copolymer of such an α-olefin with another α-olefinhaving from 2 to 20 carbon atoms such as ethylene, propylene, 1-butene,3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene or1-decene, or with a vinyl compound such as vinyl acetate, acrylic acid,methacrylic acid, an acrylate, a methacrylate, vinyl chloride orstyrene. Specifically, it may, for example, be an ethylene resin such asan ethylene homopolymer such as a low, intermediate or high densitypolyethylene, an ethylene/propylene copolymer, an ethylene/1-butenecopolymer, an ethylene/4-methyl-1-pentene copolymer, anethylene/1-hexene copolymer, an ethylene/1-octene copolymer, anethylene/vinyl acetate copolymer, an ethylene/acrylic acid copolymer, anethylene/methacrylic acid copolymer or an ethylene/ethyl acrylatecopolymer, a propylene resin such as a propylene homopolymer, apropylene/ethylene copolymer or a propylene/ethylene/1-butene copolymer,and a 1-butene resin such as a 1-butene homopolymer, a 1-butene/ethylenecopolymer or a 1-butene/propylene copolymer.

Further, the polyamide resin may, for example, be a polymer of a lactamsuch as butyrolactam, δ-valerolactam, ε-caprolactam, enantholactam orω-lauryllactam, a polymer of an amino acid such as 6-amino caproic acid,7-amino heptanoic acid, 8-amino octanoic acid, 9-amino nonanoic acid,11-amino undecanoic acid or 12-amino dodecanoic acid, a polycondensateof a diamine, such as an aliphatic diamine such as 1,4-butane diamine,1,5-pentane diamine, 1,5-hexane diamine, 1,6-hexane diamine, 1,9-nonanediamine, 1,11-undeca diamine, 1,12-dodecane diamine orα,ω-diaminopolypropylene glycol, an alicyclic diamine such as 1,3- or1,4-bis(aminomethyl)cyclohexane or bis(p-aminocyclohexylmethane), or anaromatic diamine such as m- or p-xylylene diamine, with a dicarboxylicacid, such as an aliphatic dicarboxylic acid such as glutaric acid,adipic acid, suberic acid, sebacic acid or dodecanoic diacid, analicyclic dicarboxylic acid such as cyclohexane dicarboxylic acid, or anaromatic dicarboxylic acid such as terephthalic acid or isophthalicacid, or a copolymer thereof. Specifically, for example, nylon 4, nylon6, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 66, nylon 69,nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon6/66, nylon 6/610, nylon 6/12, nylon 6/6T or nylon 6I/6T may bementioned.

In the present invention, the above crystalline thermoplastic resin maybe incorporated to the polyester resin by a common method such as amethod of directly adding and melt mixing or a method of adding and meltmixing as a master batch the above crystalline thermoplastic resin tothe above polyester resin so that its content becomes within theabove-mentioned range. Otherwise, a method may be employed wherein theabove crystalline thermoplastic resin is directly added as a powder at aproduction stage of the above polyester resin, for example, at any stageof e.g. during the melt polycondensation (the starting materials,slurry, catalyst, etc.), immediately after the melt polycondensation,immediately after the preliminary crystallization, during the solidphase polycondensation or immediately after the solid phasepolycondensation, or during a period after the production stage untilthe molding stage, or a liquid such as water having the powder dispersedtherein, is contacted with the polyester resin chips, a gas such as airhaving the powder included, is contacted with the polyester resin chips,or the polyester resin chips are contacted to a component made of thecrystalline thermoplastic resin under a flowing condition, followed bymelt kneading. Among the latter methods, a method is preferred in whichthe crystalline thermoplastic resin is incorporated to air for pneumatictransportation at the time of pneumatic transportation to a preliminarycrystallization machine or at the time of pneumatic transportation to asolid polycondensation tank, of chips of the polyester resin after themelt polycondensation, or at the time of pneumatic transportation to astorage tank or at the time of pneumatic transportation to a moldingmachine, of chips after the solid phase polycondensation.

Further, in the present invention, the polyester resin may contain, forexample, an ultraviolet absorber of e.g. a benzophenone type such as2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone,2,2′-dihydroxy-4-methoxybenzophenone or2,2′-dihydroxy-4,4′-dimethoxybenzophenone, a benzotriazole type such as2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-butylphenyl)benzotriazole,2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-t-amylphenyl)benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole or2-(2′-hydroxy-3′,5′-di-t-butylphenyl)-5-chlorobenzotriazole, asalicylate type such as phenyl salicylate, p-t-butylphenyl salicylate orp-octylphenyl salicylate, or a cyanoacrylate type such as2-ethylhexyl-2-cyano-3,3′-diphenylacryalte, and an antioxidant, aphotostabilizer, an antistatic agent, a lubricant, a blocking preventiveagent, an antifogging agent, a nucleating agent, a plasticizer, acolorant, a filler, etc.

The polyester resin of the present invention may, for example, be moldedinto a preform by injection molding, followed by stretch blow molding,or molded into a parison by extrusion, followed by blow molding, toobtain a bottle or the like, or it may be formed into a sheet byextrusion, followed by heat forming to obtain a tray, a container or thelike, or said sheet may be biaxially stretched to obtain a film or thelike, which will be particularly useful in the field of packagingbeverage products. Among them, it is particularly suitable for moldingthe preform obtained by injection molding into a bottle by a biaxiallystretching blow molding method, and it is suitable, for example, for acontainer for e.g. a carbonated beverage, an alcoholic beverage, or aliquid seasoning such as soy sauce, a regular sauce, Japanese sweet ricewine for cooking or dressing, or after heat setting, for a containerwhich is required to have an aroma-retention property and an ultravioletshielding property and which is required to be free from an influenceover the taste, fragrance, etc., of a beverage such as a fruit juicebeverage, a vitamin beverage, a flavor tea or mineral water.

Now, the present invention will be described in further detail withreference to Examples. However, the present invention is by no meansrestricted by the following Examples.

EXAMPLE 1

Slurries of 43 kg (260 mol) of terephthalic acid and 19 kg (312 mol) ofethylene glycol were continuously supplied over a period of 4 hours toan esterification reaction tank having about 60 kg of bis(hydroxyethyl)terephthalate previously charged and maintained at a temperature of 250°C. and a pressure of 1.2×10⁵ Pa, and even after completion of thesupply, the esterification reaction was further carried out for onehour. About one half of this esterification reaction product wastransferred to a polycondensation tank.

Then, to the polycondensation tank to which the esterification reactionproduct was transferred, from its pipe, ethyl acid phosphate, magnesiumacetate and tetra-n-butoxy titanium were sequentially added in theirethylene glycol solutions, respectively, with intervals of 5 minutes, sothat 0.387 mol of phosphorus atoms (P), 0.062 mol of magnesium atoms(Mg) and 0.063 mol of titanium atoms (Ti) would remain per 1 ton of theresulting polyester resin. Then, the interior of the system was heatedfrom 250° C. to 280° C. over a period of 2 hours and 30 minutes, and atthe same time, the pressure was reduced from normal pressure to 4×10² Paover a period of one hour, and while maintaining the same pressure, meltpolycondensation was carried out for a period of time until theintrinsic viscosity of the obtained resin became 0.55 dl/g. The polymerwas withdrawn in the form of a strand from the discharge outlet providedat the bottom of the polycondensation tank, cooled with water and thencut into chips to obtain about 50 kg of a polyethylene terephthalateresin.

Then, the obtained polyester resin chips were continuously supplied intoan agitation crystallizer maintained at about 160° C. so that theretention time would be about 5 minutes, for crystallization, then driedat 160° C. for 2 hours in a nitrogen stream of 40 l/min in an inert oven(“IPHH-201 model”, manufactured by ESPEC), and heated at 210° C. for aperiod of time until the intrinsic viscosity became 0.74 dl/g, for solidphase polycondensation.

With respect to the obtained polyester resin chips, the contents ofcopolymerizable components, the contents of metal atoms of therespective metal compounds, the intrinsic viscosity ([η]), the colorcoordinate value b as the color tone and the cyclic trimer content (CT)were measured by the following methods, and the results are shown inTable 1.

Content of Copolymerizable Component

With respect to a solution having a resin sample dissolved at aconcentration of 3 wt % in a mixed solvent of deuteratedchloroform/hexafluoroisopropanol (weight ratio: 7/3), ¹H-NMR wasmeasured by a nuclear magnetic resonance apparatus (“JNM-EX270 model”,manufactured by Nippon Denshi K.K.), and the respective peaks wereidentified, whereupon from the integral value of a peak, the content ofthe copolymerizable component was calculated.

Contents of Metal Atoms

2.5 g of a resin sample was ashed and completely decomposed by hydrogenperoxide in the presence of sulfuric acid in accordance with a usualmethod and then adjusted by distilled water to a constant volume of 50ml, and with respect to this sample, quantitative analysis was carriedout by means of a plasma emission spectrometer (ICP-AES “JY46P model”,manufactured by JOBIN YVON COMPANY), whereupon the molar amount per 1ton of the polyester resin was calculated.

Intrinsic Viscosity ([η])

0.25 g of a freeze-pulverized resin sample was dissolved at aconcentration (c) of 1.0 g/dl in a mixed solvent ofphenol/tetrachloroethane (weight ratio: 1/1), at 110° C. for 30 minutesin the case of a melt polycondensate resin, or at 120° C. for 30 minutesin the case of a solid phase polycondensate resin, whereupon by means ofan Ubbellohde capillary viscometer, the relative viscosity (ηrel) to thesolvent was measured at 30° C. A ratio (ηsp/c) of the specific viscosity(ηsp) obtained from this relative viscosity (ηrel)−1, to theconcentration (c), was obtained. In a similar manner, the correspondingratios (ηsp/c) were obtained when the concentration (c) was changed to0.5 g/dl, 0.2 g/dl and 0.1 g/dl, respectively. From these values, aratio (n sp/c) when the concentration (c) was extrapolated to be 0, wasobtained as the intrinsic viscosity [η] (dl/g)

Color Tone

A resin sample was filled into a cylindrical powder calorimetric cellhaving an inner diameter of 36 mm and a depth of 15 mm to be flush, andby means of a calorimetric color difference meter (“ND-300A”,manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD.), color coordinateb of the Hunter's color difference formula in the Lab color system asdisclosed in Reference 1 of JIS Z8730, was obtained as a simple averagevalue of values measured at four positions by rotating the cell every90° by a reflection method.

Cyclic Trimer Content (CT)

4.0 mg of a resin sample was accurately weighted and dissolved in 2 mlof a mixed solvent of chloroform/hexafluoroisopropanol (volume ratio:3/2), and then further diluted by an addition of 20 ml of chloroform.Then, 10 ml of methanol was added thereto for reprecipitation, followedby filtration to obtain a filtrate, which was evaporated to dryness.Then, the residue was dissolved in 25 ml of dimethylformamide. Theamount of a cyclic trimer (cyclotriethylene terephthalate) in thissolution was quantitatively analyzed by liquid chromatography (“LC-10A”,manufactured by Shimadzu Corporation).

Then, the obtained resin was dried at 160° C. for at least 16 hours in avacuum dryer (“DP-41 model”, manufactured by YAMATO CHEMICAL INDUSTRYCO., LTD). Then, by an injection molding machine (“M-70AII-DM”,manufactured by Meiki Co., Ltd.), a stepped molded plate having theshape as shown in FIG. 1 and having a size of 50 mm×100 mm andthicknesses of six steps ranging from 6 mm to 3.5 mm in a transversedirection with each step being 0.5 mm, was injection-molded at acylinder temperature of 280° C. under a back pressure of 5×10⁵ Pa at aninjection rate of 40 cc/sec under a dwell pressure of 35×10⁵ Pa at amold temperature of 25° C. and with a molding cycle of about 75 seconds.Further, in FIG. 1, G indicates a gate portion.

With respect to the molded plate thus obtained, the absorbance at awavelength of 395 nm and 500 nm, and the temperature-risingcrystallization temperature (Tc) were measured by the following methods,and the results are shown in Table 1.

Absorbance

The portion having a thickness of 3.5 mm (portion A+B in FIG. 1) in themolded plate, was measured by means of a ultraviolet visible lightspectrophotometer (“UV-2400”, manufactured by Shimadzu Corporation) at ascanning speed adjusted to be a low speed mode (127 nm/min within awavelength range of from 300 to 800 nm with a slit width of 5 nm at asampling pitch of 0.5 nm by a transmission mode, whereby the differencesfrom the absorbance at a wavelength of 800 nm, of the absorbances atwavelengths of 395 nm and 500 nm, were obtained.

Temperature-Rising Crystallization Temperature (Tc)

The forward end portion (portion A in FIG. 1) having a thickness of 3.5mm in the molded plate, was cut out and dried at 40° C. for 3 days by avacuum dryer, whereupon a sample cut out from the non-surface portionwas used, and about 10 mg thereof was accurately weighed and sealed inby means of an aluminum oven pan and a pan cover (normal pressure type,“P/N SSC000E030” and “P/N SSC000E032”, manufactured by Seiko DenshiK.K.). By means of a differential scanning calorimeter (“DSC220C”,manufactured by Seiko K.K.), the sample was heated from 20° C. to 285°C. at a rate of 20° C./min in a nitrogen stream, and the crystallizationpeak temperature observed during the temperature rise, was measured.

Separately, the obtained polyester resin chips were dried at 130° C. for10 hours by a vacuum dryer. Then, by an injection molding machine(“FE-80S”, manufactured by Nissei Plastic Industrial Co., Ltd.), apreform of a test tube shape having an outer diameter of 29.0 mm, aheight of 165 mm, an average wall thickness of 3.7 mm and a weight of 60g, was injection-molded at a cylinder temperature of 280° C. under aback pressure of 5×10⁵ Pa at an injection rate of 45 cc/sec under adwell pressure of 30×10⁵ Pa at a mold temperature of 20° C. with amolding cycle of about 4.0 seconds.

Such preforms were heated for 70 seconds in a near infrared rayirradiation furnace equipped with a quartz heater, then left at roomtemperature for 25 seconds and then introduced into a blow mold set at160° C. and subjected to blow molding under a blow pressure of about7×10⁵ Pa for one second and then under a blow pressure of about 30×10⁵Pa for 40 seconds for heat setting, while stretching it in the heightdirection by a stretching rod, followed by cooling in air to obtain 500bottles having an outer diameter of about 95 mm, a height of about 305mm, an average wall thickness of the body portion of about 0.37 mm, aweight of about 60 g and an internal capacity of about 1.5 l. Withrespect to the obtained 498th to 500th bottles, the aroma-retentionproperty was measured and evaluated by the following method, and theresults are shown in Table 1.

Aroma-Retention Property

In a bottle, a 100% orange juice was filled in a hot state, tightlysealed with a cap and stored at 10° C. for one month, whereupon the capwas removed, and the aroma was subjected to a sensory test by comparingit with a case where the orange juice was stored under the sameconditions in a glass bottle, whereby evaluation was made under thefollowing standards.

◯: there was no difference in aroma from the glass bottle, and thearoma-retention property was good.

Δ: the aroma was weak as compared with the glass bottle, and thearoma-retention property was slightly poor.

X: the aroma was extremely weak as compared with the glass bottle, andthe aroma-retention property was inferior.

Further, with respect to the obtained 491st to 500th bottles, thesurface appearance of the body portion of each bottle was visuallyobserved and evaluated under the following standards, to evaluate themold contamination, and the results are shown in Table 1.

⊚: the surface was smooth, and no mold contamination was observed.

◯: the surface smoothness was slightly inferior, and accordingly, themold contamination was slightly observed but was not practicallyproblematic.

X: the surface was roughened, deposition of foreign matters wasobserved, and the mold contamination was substantial.

EXAMPLES 2 TO 6

The operation was carried out in the same manner as in Example 1 exceptthat the amounts of ethyl acid phosphate, magnesium acetate andtetra-n-butoxy titanium at the time of the melt polycondensation werechanged as shown in Table 1, and then results are shown in Table 1.

EXAMPLE 7

The operation was carried out in the same manner as in Example 2 exceptthat the solid phase polycondensation polyester resin obtained inExample 2 was further subjected to water treatment by immersing it inhot water of 90° C. for two hours, and the results are shown in Table 1.

EXAMPLE 8

The operation was carried out in the same manner as in Example 7 exceptthat the polyester resin obtained in Example 7 was used, and a lowdensity polyethylene was added at the time of the injection molding ofthe stepped molding plate and at the time of the injection molding ofthe preform, and the results are shown in Table 1.

COMPARATIVE EXAMPLE 1

The operation was carried out in the same manner as in Example 1 exceptthat at the time of the melt polycondensation, ethyl acid phosphate,magnesium acetate and antimony trioxide were sequentially added in theirethylene glycol solutions, respectively, with intervals of 5 minutes,and the respective amounts were adjusted as shown in Table 1, and theresults are shown in Table 1.

COMPARATIVE EXAMPLE 2

The operation was carried out in the same manner as in Example 1 exceptthat at the time of the melt polycondensation, orthophosphoric acid andgermanium dioxide were sequentially added in their ethylene glycolsolutions, respectively, with intervals of 5 minutes, and the respectiveamounts were adjusted as shown in Table 1, and the results are shown inTable 1.

COMPARATIVE EXAMPLE 3

The operation was carried out in the same manner as in ComparativeExample 2 except that the amount of germanium dioxide was changed, andthe obtained solid phase polycondensation polyester resin was furthersubjected to water treatment by dipping it in hot water at 90° C. for 4hours, and the results are shown in Table 1.

COMPARATIVE EXAMPLE 4

The operation was carried out in the same manner as in Example 1 exceptthat at the time of the melt polycondensation, tetra-n-butoxy titanium,magnesium acetate and ethyl acid phosphate were sequentially added intheir ethylene glycol solutions, respectively, with intervals of 5minutes, and the respective amounts were adjusted as shown in Table 1,and the results are shown in Table 1. TABLE 1 Examples 1 2 3 4 5 6 7 8Copolymerizable Diethylene glycol 1.8 1.7 1.8 1.6 1.6 1.7 1.7 1.7components (mol % based on diol) Contents of Titanium atoms (T) (mol/t)0.063 0.063 0.063 0.063 0.063 0.125 0.063 0.063 metal atoms Magnesiumatoms (M) (mol/t) 0.062 0.123 0.247 0.123 0.123 0.247 0.123 0.123Germanium atoms (Ge) (mol/t) Antimony atoms (Sb) (mol/t) Phosphorusatoms (P) (mol/t) 0.387 0.387 0.387 0.194 0.065 0.387 0.387 0.387 P/T(mol/mol) 6.14 6.14 6.14 3.08 1.03 3.10 6.14 6.14 M/T (mol/mol) 0.981.95 3.92 1.95 1.95 1.98 1.95 1.95 P/M (mol/mol) 6.24 3.15 1.57 1.580.53 1.57 3.15 3.15 P/(T + M) (mol/mol) 3.10 2.08 1.25 1.04 0.35 1.042.08 2.08 Resin chips Intrinsic viscosity [η] (dl/g) 0.74 0.75 0.75 0.730.74 0.74 0.75 0.75 Color coordinate b +2.6 +1.8 +2.4 +2.4 +3.4 +4.7+1.8 +1.8 Cyclic trimer (wt %) 0.29 0.32 0.33 0.29 0.27 0.22 0.32 0.32content (CT) Stepped molded Absorbance 395 nm 0.16 0.11 0.15 0.14 0.190.26 0.11 0.11 plate 500 nm 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02Temperature-rising (° C.) 165 166 165 172 178 165 164 161crystallization temperature (Tc) Bottle Aroma-retention property ◯ ◯ ◯ ◯◯ ◯ ◯ ◯ Mold contamination property ◯ ◯ ◯ ◯ ◯ ◯ ⊚ ⊚ Comparative Example1 2 3 4 Copolymerizable Diethylene glycol 3.5 2.5 2.5 3.8 components(mol % based on diol) Contents of Titanium atoms (T) (mol/t) 1.086 metalatoms Magnesium atoms (Mg) (mol/t) 2.057 2.180 Germanium atoms (Ge)(mol/t) 0.551 0.716 Antimony atoms (Sb) (mol/t) 1.372 Phosphorus atoms(P) (mol/t) 2.906 0.969 0.969 0.549 P/T (mol/mol) — — — 0.5 M/T(mol/mol) — — — 2.00 P/M (mol/mol) 1.41 — — 0.25 P/(T + M) (mol/mol) — —— 0.17 Resin chips Intrinsic viscosity [η] (dl/g) 0.78 0.76 0.76 0.75Color coordinate b +0.8 +0.9 +1.2 +14.3 Cyclic trimer content (CT) (wt%) 0.40 0.42 0.32 0.34 Stepped molded Absorbance 395 nm 0.04 0.06 0.050.42 plate 500 nm 0.01 0.01 0.01 0.06 Temperature-rising (° C.) 142 168166 153 crystallization temperature (Tc) Bottle Aroma-retention propertyX Δ Δ X Mold contamination property ◯ ◯ ⊚ X

EXAMPLE 9

Using a continuous polymerization apparatus comprising a slurrypreparation tank, esterification reactors of two stages connected inseries thereto and melt polycondensation tanks of three stages connectedin series to the second stage esterification reactor, terephthalic acidand ethylene glycol were continuously supplied in a weight ratio of865:485 to the slurry preparation tank, and a 0.3 wt % ethylene glycolsolution of ethyl acid phosphate, was continuously added in such anamount that the content as phosphorus atoms (P) per 1 ton of the formedpolyester resin would be 0.194 mol, followed by stirring and mixing toobtain a slurry. This slurry was transferred to the first stageesterification reactor set for an average retention time of 4 hours in anitrogen atmosphere at 260° C. under a relative pressure of 50 kPa (0.5kg/cm²G) and then to the second stage esterification reactor set for anaverage retention time of 1.5 hours in a nitrogen atmosphere at 260° C.under a relative pressure of 5 kPa (0.05 kg/cm²G), to carry out theesterification reaction. At that time, the average esterification ratioas measured by the following method, was 85% in the first stage and 95%in the second stage.

Average Esterification Ratio

With respect to a solution having a sample dissolved at a concentrationof 3 wt % in a mixed solvent of deuteratedchloroform/hexafluoroisopropanol (weight ratio: 7/3), ¹H-NMR wasmeasured by a nuclear magnetic resonance apparatus (“JNM-EX270 model”,manufactured by Nihon Denshi K.K.), and each peak was identified. Theamount of terminal carboxyl groups (A mol/ton sample) was calculatedfrom the integral value of the peak, and by the following formula, theesterification ratio (E %) was calculated as a proportion of theesterified among all carboxyl groups of terephthalic acid units.Esterification ratio(E)=[1−A/{(1,000,000/192.2)×2}]×100

Further, at that time, via an upper pipe provided at the second stage, a0.6 wt % ethylene glycol solution of magnesium acetate tetrahydrate wascontinuously added in such an amount that the content as magnesium atoms(Mg) per 1 ton of the formed polyester resin would be 0.247 mol.

Continuously, at the time of transporting the esterification reactionproduct obtained as described above to the melt polycondensation tank,tetrabutyl titanate in the form of an ethylene glycol solution having aconcentration of titanium atoms of 0.15 wt % and a water concentrationof 0.5 wt %, was continuously added to the esterification reactionproduct in the transportation pipe in such an amount that the content astitanium atoms (Ti) per 1 ton of the formed polyester resin would be0.063 mol, and the esterification reaction product was continuouslytransferred to the first stage melt polycondensation tank set at 270° C.under an absolute pressure of 2.6 kPa (20 Torr), then to the secondstage melt polycondensation tank set at 278° C. under an absolutepressure of 0.5 kPa (4 Torr) and then to the third stage meltpolycondensation tank set at 280° C. under an absolute pressure of 0.3kPa (2 Torr), to carry out the melt polycondensation for a total of 3.17hours by adjusting the retention times in the respectivepolycondensation tanks so that the intrinsic viscosity ([η₁]) of theobtained polyester resin would be 0.56 dl/g, whereupon the product iswithdrawn in the form of a strand from a discharge outlet provided atthe bottom of the polycondensation tank, cooled with water and then cutby a cutter to obtain a polyester resin in the form of chips.

Then, the polyester resin chips obtained as described above werecontinuously supplied for crystallization to an agitationcrystallization machine held at about 160° C. in a nitrogen atmosphereso that the retention time would be about 60 minutes and thencontinuously supplied to a tower type solid polycondensation apparatusand heated at 205° C. in a nitrogen atmosphere for 19 hours for solidphase polycondensation by adjusting the retention time so that theintrinsic viscosity ([η₂]) of the obtained polyester resin would be 0.75dl/g. The intrinsic viscosity ([η₁]) of the above melt polycondensateresin and the intrinsic viscosity ([η₂]) of the solid polycondensateresin, were measured by the above-mentioned method.

Further, the melt polycondensation rate (V₁) as a value obtained bydividing the intrinsic viscosity ([η₁]) of the above melt polycondensateresin by the melt polycondensation time, the solid phasepolycondensation rate (V₂) as a value obtained by dividing thedifference ([η₂]−[η₁]) between the above intrinsic viscosity ([η₂]) ofthe above solid polycondensate resin and the intrinsic viscosity ([η₁])of the above melt polycondensate resin, by the solid phasepolycondensation time, and the ratio (V₂/V₁) of the solid phasepolycondensation rate (V₂) to the melt polycondensation rate (V₁), werecalculated, respectively, and the results are shown in Table 2.

Further, with respect to the obtained solid phase polycondensate resinchips, the contents of titanium atoms (Ti), magnesium atoms (Mg) andphosphorus atoms (P) of the titanium component, the magnesium componentand the phosphorus component, respectively, per 1 ton of the resin, weremeasured by the above-mentioned methods, and the results are shown inTable 2.

Further, with respect to the obtained solid phase polycondensate resinchips, the copolymerized amount of diethylene glycol, the cyclic trimercontent (CT) and the color coordinate value b as the color tone, weremeasured by the above-mentioned methods, and the acetaldehyde content(AA₁) was measured by the following method. The results are shown inTable 2.

Acetaldehyde Content (AA₁)

5.0 g of a resin sample was accurately weighed and sealed in togetherwith 10 ml of pure water in a micro bomb having an internal capacity of50 ml under sealing with nitrogen, whereupon heat extraction was carriedout at 160° C. for 2 hours. The amount of acetaldehyde in the extractedsolution was quantitatively analyzed by gas chromatography (“GC-14A”,manufactured by Shimadzu Corporation) using isobutyl alcohol as theinternal standard.

Then, the obtained resin was dried at 160° C. for 4 hours in a nitrogenstream of 40 l/min in an inert oven (“IPHH-201 model”, manufactured byESPEC COMPANY), and then, by an injection molding machine (“M-70AII-DM”,manufactured by Meiki Co., Ltd.), a stepped molded plate having a shapeshown in FIG. 1, was injection-molded at a cylinder temperature of 280°C. under a back pressure of 5×10⁵ Pa at an injection rate of 40 cc/secunder a dwell pressure of 35×10⁵ Pa at a mold temperature of 25° C. witha molding cycle of about 75 seconds.

With respect to the molded plate, the absorbances at wavelengths of 395nm and 500 nm were measured by the above-mentioned method, and further,the acetaldehyde content (AA₂) and the haze, were measured by thefollowing methods. The results are shown in Table 2.

Acetaldehyde Content (AA₂)

Using samples cut out in the form of chips of about 4×4 mm from the rearend portion having a thickness of 3.5 mm (portion B in FIG. 1) in themolded plate, the measurement was carried out by the same method asdescribed above.

Haze

With respect to the portion having a thickness of 5.0 mm (portion C inFIG. 1) in the molded plate, the haze was measured by means of a hazemeter (“NDH-300A”, manufactured by NIPPON DENSHOKU INDUSTRIES CO.,LTD.).

Separately, the obtained polyester resin chips were dried at 130° C. for10 hours in a vacuum dryer. Then, by an injection molding machine(“FE-80S”, manufactured by Nissei Plastic Industrial Co., Ltd.), apreform of a test tube shape having an outer diameter of 29.0 mm, aheight of 165 mm, an average wall thickness of 3.7 mm and a weight ofabout 60 g, was injection-molded at a cylinder temperature of 280° C.under a back pressure of 5×10⁵ Pa at an injection rate of 45 cc/secunder a dwell pressure of 30×10⁵ Pa at a mold temperature of 20° C. witha molding cycle of about 40 seconds.

The obtained preform was heated for 70 seconds in a near infrared rayirradiation furnace equipped with a quartz heater and then left to standat room temperature for 25 seconds. Then, it was introduced into a blowmold set at 130° C. and blow-molded under a blow pressure of 7×10⁵ Pafor one second and further under a blow pressure of 30×10⁵ Pa for 5seconds, while stretching in the height direction by an stretching rod,heat-set and cooled in air to mold a bottle having an outer diameter ofabout 95 mm, a height of about 305 mm, an average wall thickness of thebody portion of about 0.35 mm, a weight of about 60 g and an internalcapacity of about 1.5 l.

With respect to the obtained bottle, the aroma-retention property andthe mold contamination were measured and evaluated by theabove-mentioned methods, and further, the acetaldehyde odor wasevaluated by the following method. The results are shown in Table 2.

Acetaldehyde Odor of the Bottle

The bottle was heated in an oven at 50° C. for one hour, whereupon theacetaldehyde odor was examined by a sensory test and evaluated by fivestages ranging from 5 (acetaldehyde odor very little) to 1 (acetaldehydeodor assails ones nostrils).

EXAMPLES 10 TO 23, AND COMPARATIVE EXAMPLES 5 to 7

Polyester resin chips were prepared in the same manner as in Example 9except that the copolymerizable component and its amount, the amountsand order for addition of the phosphorus compound, the magnesiumcompound and the titanium compound, the concentration of titanium atomsand the water concentration in the ethylene glycol solution of thetitanium compound, and the melt polycondensation time and the solidphase polycondensation time, were changed as identified in Table 2, andevaluated in the same manner. The results are shown in Table 2. InComparative Example 5, phosphorous acid instead of ethyl acid phosphate,cobalt acetate tetrahydrate instead of magnesium acetate tetrahydrateand titanium potassium oxalate instead of tetrabutyl titanate, were usedand added in the order of titanium potassium oxalate, then cobaltacetate tetrahydrate and then phosphorous acid. In Comparative Example7, orthophosphoric acid was used instead of ethyl acid phosphate, andthe order of addition was tetrabutyl titanate, then magnesium acetatetetrahydrate and then orthophosphoric acid. TABLE 2 Examples 9 10 11 1213 14 15 16 17 Copolymerizable Diethylene glycol 2.2 2.2 2.2 2.2 2.2 2.21.7 2.2 2.2 components (mol % based on diol) Isophthalic acid (mol %based 1.8 on dicarboxylic acid) Ethylene Concentration of titanium atoms(wt %) 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.40 0.15 glycol solution ofWater concentration (wt %) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1.5 0.03 thetitanium compound Contents of Titanium atoms (T) (mol/t) 0.063 0.0630.063 0.063 0.063 0.125 0.063 0.063 0.063 metal atoms Magnesium atoms(M) (mol/t) 0.247 0.123 0.370 0.247 0.247 0.247 0.247 0.247 0.247 Cobaltatoms (M) (mol/t) Phosphorus atoms (P) (mol/t) 0.194 0.194 0.194 0.0650.387 0.387 0.194 0.194 0.194 P/T (mol/mol) 3.1 3.1 3.1 1.0 6.2 3.1 3.13.1 3.1 M/T (mol/mol) 3.9 2.0 5.9 3.9 3.9 2.0 3.9 3.9 3.9Polycondensation Melt polycondensation time (hr) 3.17 3.33 3.00 3.003.33 3.00 3.17 3.25 3.25 rate Intrinsic viscosity [η₁] (dl/g) 0.56 0.560.56 0.56 0.56 0.56 0.56 0.56 0.56 Polycondensation rate (dl/g/hr) 0.1770.168 0.187 0.187 0.168 0.187 0.177 0.172 0.172 (V₁) Solid phasepolycondensation (hr) 19 20 22 18 28 18 18 20 20 time Intrinsicviscosity [η₂] (dl/g) 0.75 0.75 0.75 0.77 0.77 0.76 0.75 0.75 0.75Polycondensation rate (V₂) (dl/g/hr) 0.010 0.010 0.009 0.012 0.008 0.0110.011 0.010 0.010 V₂/V₁ 0.057 0.060 0.046 0.063 0.045 0.060 0.060 0.0550.055 Resin chips Acetaldehyde content (AA₁) (ppm) 3 4 4 3 4 4 3 4 4Cyclic trimer content (CT) (wt %) 0.28 0.28 0.32 0.24 0.24 0.19 0.270.28 0.28 Color coordinate b +2.2 +2.4 +2.2 +3.4 +2.4 +4.7 +2.2 +2.4+2.4 Stepped Absorbance 395 nm 0.16 0.14 0.16 0.20 0.15 0.26 0.16 0.160.16 molded plate 500 nm 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02Acetaldehyde content (AA₂) (ppm) 16 18 15 20 14 20 14 16 16 Haze (%) 7 88 8 7 8 4 12 15 Bottle Aroma-retention property ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Moldcontamination property ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Acetaldehyde odor 4 4 4 4 5 4 54 4 Comparative Examples Examples 18 19 20 21 22 23 5 6 7Copolymerizable Diethylene glycol 2.2 2.2 2.2 2.2 2.2 2.2 3.1 2.8 3.8components (mol % based on diol) Isophthalic acid (mol % based ondicarboxylic acid) Ethylene Concentration of titanium atoms (wt %) 0.150.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 glycol Water concentration (wt%) 0.5 0.5 0.5 0.5 0.5 0.5 0.03 0.03 0.03 solution of the titaniumcompound Contents of Titanium atoms (T) (mol/t) 0.010 0.313 0.063 0.0630.063 0.063 0.125 0.021 1.086 metal atoms Magnesium atoms (Mg) (mol/t)0.247 0.247 0.740 0.247 0.247 1.550 2.180 Cobalt atoms (M) (mol/t) 1.033Phosphorus atoms (P) (mol/t) 0.387 0.387 0.194 0.194 0.775 0.494 1.0700.549 P/T (mol/mol) 37.1 1.2 3.1 3.1 0 12.4 3.9 51.2 0.5 M/T (mol/mol)23.6 0.8 0 11.7 3.9 3.9 8.3 74.2 2.0 Polycondensation Meltpolycondensation time (hr) 4.00 2.00 3.67 2.75 2.83 4.00 3.50 3.50 2.00rate Intrinsic viscosity [η₁] (dl/g) 0.56 0.56 0.56 0.56 0.56 0.56 0.560.56 0.56 Polycondensation rate (V₁) (dl/g/hr) 0.140 0.280 0.153 0.2040.198 0.140 0.160 0.160 0.280 Solid phase polycondensation (hr) 38 12 2632 15 42 43 42 12 time Intrinsic viscosity [η₂] (dl/g) 0.76 0.76 0.750.75 0.77 0.77 0.75 0.75 0.75 Polycondensation rate (V₂) (dl/g/hr) 0.0050.017 0.007 0.006 0.014 0.005 0.004 0.005 0.016 V₂/V₁ 0.038 0.060 0.0480.029 0.071 0.036 0.028 0.029 0.057 Resin chips Acetaldehyde content(AA₁) (ppm) 4 11 4 4 3 4 8 3 11 Cyclic trimer content (CT) (wt %) 0.550.17 0.28 0.56 0.21 0.45 0.88 0.49 0.34 Color coordinate b +0.6 +11.3+2.4 +2.4 +4.2 +2.4 −2.3 +2.2 +14.3 Stepped Absorbance 395 nm 0.09 0.310.20 0.21 0.27 0.10 0.06 0.06 0.42 molded plate 500 nm 0.01 0.05 0.030.03 0.04 0.02 0.01 0.01 0.06 Acetaldehyde content (AA₂) (ppm) 18 30 2114 28 13 27 23 35 Haze (%) 7 12 9 8 12 7 8 8 70 Bottle Aroma-retentionproperty ◯ ◯ ◯ ◯ ◯ ◯ X ◯ X Mold contamination property ◯ ◯ ◯ ◯ ◯ ◯ X ◯ XAcetaldehyde odor 4 1 3 5 2 5 2 3 1

INDUSTRIAL APPLICABILITY

According to the present invention, it is possible to provide apolyester resin, whereby a molded product excellent in a gas barrierproperty and also excellent in an ultraviolet shielding property, colortone, etc., and which is particularly suitable for molding a bottle fore.g. a beverage required to have an aroma-retention property and furtherto provide a polyester resin, whereby the acetaldehyde content in amolded product is reduced to eliminate an influence over the taste,aroma, etc. of the content, and a process for its production, wherebythe polycondensability is improved.

1.-15. (canceled)
 16. A polyester resin produced by polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component, and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table, via anesterification reaction or an ester exchange reaction, wherein saidpolyester resin is obtained by melt polycondensation wherein theintrinsic viscosity ([η₁]) ranges from 0.35 to 0.75 dl/g as a valuemeasured at 30° C. in a solution in a mixed solvent ofphenol/tetrachloroethane (weight ratio: 1/1) and wherein the meltpolycondensation velocity (V₁) as a value obtained by dividing theintrinsic viscosity ([η₁]) of the resulting polyester resin by thereaction time, is at least 0.15 dl/g/hr.
 17. The polyester resinaccording to claim 16, wherein the temperature-rising crystallizationtemperature (Tc) of the resin in the molded product after the injectionmolding at 280° C., is from 150 to 180° C.
 18. The polyester resinaccording to claim 16, wherein the resin before the injection molding isone having an intrinsic viscosity ([η]) of from 0.70 to 0.90 dl/g and acolor coordinate value b of the Hunter's color difference formula of notmore than
 4. 19. The polyester resin according to claim 16, wherein thecontent of the compound (1) is from 0.002 to 1 mol as the total amount(T) of atoms of the compound (1) per 1 ton of the polyester resin. 20.The polyester resin according to claim 19, which is one polycondensed inthe coexistence of (2) a compound of at least one element selected fromthe group consisting of metal elements of Group Ia of the periodictable, elements of Group IIa of the periodic table, manganese, iron andcobalt, and (3) a phosphorus compound, wherein the content of thecompound (2) is from 0.04 to 5 mols as the total amount (M) of atoms ofthe compound (2) per 1 ton of the polyester resin, and the content ofthe compound (3) is from 0.02 to 4 mols as the total amount (P) of atomsof the compound (3) per 1 ton of the polyester resin.
 21. The polyesterresin according to claim 20, wherein the contents of the respectivecompounds (1), (2) and (3) are from 0.02 to 0.2 mol as the total amount(T) of atoms of the compound (1), from 0.04 to 0.6 mol as the totalamount (M) of atoms of the compound (2) and from 0.02 to 0.4 mol as thetotal amount (P) of atoms of the compound (3), per 1 ton of thepolyester resin, the acetaldehyde content (AA₁) is not more than 5.0ppm, the acetaldehyde content (AA₂) of the resin in a molded productafter injection-molded at 280° C. is not more than 20 ppm, and the hazeof a molded product with a thickness of 5 mm after the injection moldingat 280° C. is not more than 10%.
 22. The polyester resin according toclaim 16, wherein the compound (1) is a titanium compound, the compound(2) is a magnesium compound, and the compound (3) is a phosphoric acidester.
 23. The polyester resin according to claim 16, wherein, as adicarboxylic acid component, from 0.1 to 3 mol % of isophthalic acid orits ester-forming derivative based on the total dicarboxylic acidcomponent, and as a diol component, from 1 to 3 mol % of diethyleneglycol based on the total diol component, are copolymerized,respectively.
 24. A process for producing the polyester resin accordingto claim 16, which comprises polycondensing a dicarboxylic acidcomponent containing terephthalic acid or its ester-forming derivativeas the main component, and a diol component containing ethylene glycolas the main component in the presence of (1) a compound of at least onemember selected from the group consisting of titanium group elements inGroup 4A of the periodic table, (2) a compound of at least one elementselected from the group consisting of metal elements of Group Ia of theperiodic table, elements of Group IIa of the periodic table, manganese,iron and cobalt, and (3) a phosphorus compound, via an esterificationreaction or an ester exchange reaction, characterized in that theamounts of the respective compounds (1), (2) and (3) are such amountsthat their contents will be from 0.02 to 0.2 mol as the total amount (T)of atoms of the compound (1), from 0.04 to 0.6 mol as the total amount(M) of atoms of the compound (2) and from 0.02 to 0.4 mol as the totalamount (P) of atoms of the compound (3), per 1 ton of the polyesterresin.
 25. The process for producing a polyester resin according toclaim 24, wherein the ratio (P/T) of the total amount (P) of atoms ofthe compound (3) to the total amount (T) of atoms of the compound (1),is from 0.1 to
 10. 26. The process for producing a polyester resinaccording to claim 24, wherein the ratio (M/T) of the total amount (M)of atoms of the compound (2) to the total amount (T) of atoms of thecompound (1), is from 0.1 to
 10. 27. The process for producing apolyester resin according to claim 24, wherein the order for addition ofthe respective compounds (1), (2) and (3) to the reaction system is (3),then (2) and then (1).
 28. The process for producing a polyester resinaccording to claim 24, wherein the compound (1) is a titanium compound,the compound (2) is a magnesium compound, and the compound (3) is aphosphoric acid ester.
 29. The process for producing a polyester resinaccording to claim 28, wherein the titanium compound is added to thereaction system in the form of an ethylene glycol solution having atitanium atom concentration of from 0.01 to 0.3 wt % and a waterconcentration of from 0.1 to 1 wt %.
 30. The process for producing apolyester resin according to claim 24, wherein from 0.1 to 3 mol % ofisophthalic acid or its ester-forming derivative is used based on thetotal dicarboxylic acid component.
 31. A process for producing thepolyester resin of claim 16, which comprises polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the Periodic Table, via anesterification reaction or an ester exchange reaction, wherein the abovecompound (1) is added to an esterification reaction tank for a finalstage in a multi-stage reaction apparatus or to an esterificationreaction or ester exchange reaction product in a stage fortransportation to a melt polycondensation step.
 32. The process forproducing a polyester resin according to claim 31 which comprisespolycondensing terephthalic acid and ethylene glycol in the presence of(1) a compond of at least one member selected from the group consistingof titanium group elements in Group 4A of the Periodic Table, via anesterification reaction, wherein the above compound (1) is added to anesterification reaction tank for a final stage in a multi-stage reactionapparatus or to an esterification reaction product in a stage fortransportation to a melt polycondensation step.
 33. The process forproducing a polyester resin according to claim 31, wherein the compound(1) is added at such a stage as an esterification rate of anesterification reaction or ester exchange reaction product becomes atleast 90%.
 34. The process for producing a polyester resin according toclaim 31, wherein the compound (1) is added to an esterificationreaction product in a stage for transportation to a meltpolycondensation step.
 35. The process for producing a polyester resinaccording to claim 31, wherein the polycondensation is carried out inthe presence of (2) a compound of at least one member selected from thegroup consisting of metal elements of Group 1A of the Periodic Table,elements of Group 2A of the Periodic Table, manganese, iron and cobaltand (3) a phosphorus compound.
 36. The process for producing a polyesterresin according to claim 35, wherein a compound of at least one elementselected from the group consisting of metal elements of Group 1A of thePeriodic Table, elements of Group 2A of the Periodic Table, manganese,iron and cobalt is added to an esterification reaction tank for a finalstage in a multistage reaction apparatus.
 37. The process for producinga polyester resin according to claim 31, wherein the compound (1) is atitanium compound.
 38. A polyester resin produced by polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component, and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table, via anesterification reaction or an ester exchange reaction, wherein saidpolyester resin is obtained by solid phase polycondensation is whereinthe intrinsic viscosity ([η₂]) ranges from 0.70 to 0.90 dl/g as a valuemeasured at 30° C. in a solution in a mixed solvent ofphenol/tetrachloroethane (weight ratio: 1/1) and wherein the solid phasepolycondensation velocity (V₂) as a value obtained by dividing thedifference ([η₂]−[η₁]) between the intrinsic viscosity ([η₂]) of theobtainable solid phase polycondensation resin and the intrinsicviscosity ([η₁]) of the melt polycondensation resin, by the reactiontime, ranges from 0.008 to 0.015 dl/g/hr.
 39. The polyester resinaccording to claim 38, wherein the temperature-rising crystallizationtemperature (Tc) of the resin in the molded product after the injectionmolding at 280° C., is from 150 to 180° C.
 40. The polyester resinaccording to claim 38, wherein the resin before the injection molding isone having an intrinsic viscosity ([η]) of from 0.70 to 0.90 dl/g and acolor coordinate value b of the Hunter's color difference formula of notmore than
 4. 41. The polyester resin according to claim 38, wherein thecontent of the compound (1) is from 0.002 to 1 mol as the total amount(T) of atoms of the compound (1) per 1 ton of the polyester resin. 42.The polyester resin according to claim 41, which is one polycondensed inthe coexistence of (2) a compound of at least one element selected fromthe group consisting of metal elements of Group Ia of the periodictable, elements of Group IIa of the periodic table, manganese, iron andcobalt, and (3) a phosphorus compound, wherein the content of thecompound (2) is from 0.04 to 5 mols as the total amount (M) of atoms ofthe compound (2) per 1 ton of the polyester resin, and the content ofthe compound (3) is from 0.02 to 4 mols as the total amount (P) of atomsof the compound (3) per 1 ton of the polyester resin.
 43. The polyesterresin according to claim 42, wherein the contents of the respectivecompounds (1), (2) and (3) are from 0.02 to 0.2 mol as the total amount(T) of atoms of the compound (1), from 0.04 to 0.6 mol as the totalamount (M) of atoms of the compound (2) and from 0.02 to 0.4 mol as thetotal amount (P) of atoms of the compound (3), per 1 ton of thepolyester resin, the acetaldehyde content (AA₁) is not more than 5.0ppm, the acetaldehyde content (AA₂) of the resin in a molded productafter injection-molded at 280° C. is not more than 20 ppm, and the hazeof a molded product with a thickness of 5 mm after the injection moldingat 280° C. is not more than 10%.
 44. The polyester resin according toclaim 38, wherein the compound (1) is a titanium compound, the compound(2) is a magnesium compound, and the compound (3) is a phosphoric acidester.
 45. The polyester resin according to claim 38, wherein, as adicarboxylic acid component, from 0.1 to 3 mol % of isophthalic acid orits ester-forming derivative based on the total dicarboxylic acidcomponent, and as a diol component, from 1 to 3 mol % of diethyleneglycol based on the total diol component, are copolymerized,respectively.
 46. A process for producing the polyester resin accordingto claim 38, which comprises polycondensing a dicarboxylic acidcomponent containing terephthalic acid or its ester-forming derivativeas the main component, and a diol component containing ethylene glycolas the main component in the presence of (1) a compound of at least onemember selected from the group consisting of titanium group elements inGroup 4A of the periodic table, (2) a compound of at least one elementselected from the group consisting of metal elements of Group Ia of theperiodic table, elements of Group IIa of the periodic table, manganese,iron and cobalt, and (3) a phosphorus compound, via an esterificationreaction or an ester exchange reaction, characterized in that theamounts of the respective compounds (1), (2) and (3) are such amountsthat their contents will be from 0.02 to 0.2 mol as the total amount (T)of atoms of the compound (1), from 0.04 to 0.6 mol as the total amount(M) of atoms of the compound (2) and from 0.02 to 0.4 mol as the totalamount (P) of atoms of the compound (3), per 1 ton of the polyesterresin.
 47. The process for producing a polyester resin according toclaim 46, wherein the ratio (P/T) of the total amount (P) of atoms ofthe compound (3) to the total amount (T) of atoms of the compound (1),is from 0.1 to
 10. 48. The process for producing a polyester resinaccording to claim 46, wherein the ratio (M/T) of the total amount (M)of atoms of the compound (2) to the total amount (T) of atoms of thecompound (1), is from 0.1 to
 10. 49. The process for producing apolyester resin according to claim 46, wherein the order for addition ofthe respective compounds (1), (2) and (3) to the reaction system is (3),then (2) and then (1).
 50. The process for producing a polyester resinaccording to claim 46, wherein the compound (1) is a titanium compound,the compound (2) is a magnesium compound, and the compound (3) is aphosphoric acid ester.
 51. The process for producing a polyester resinaccording to claim 50, wherein the titanium compound is added to thereaction system in the form of an ethylene glycol solution having atitanium atom concentration of from 0.01 to 0.3 wt % and a waterconcentration of from 0.1 to 1 wt %.
 52. The process for producing apolyester resin according to claim 46, wherein from 0.1 to 3 mol % ofisophthalic acid or its ester-forming derivative is used based on thetotal dicarboxylic acid component.
 53. A process for producing thepolyester resin of claim 38, which comprises polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the Periodic Table, via anesterification reaction or an ester exchange reaction, wherein the abovecompound (1) is added to an esterification reaction tank for a finalstage in a multi-stage reaction apparatus or to an esterificationreaction or ester exchange reaction product in a stage fortransportation to a melt polycondensation step.
 54. The process forproducing a polyester resin according to claim 53 which comprisespolycondensing terephthalic acid and ethylene glycol in the presence of(1) a compond of at least one member selected from the group consistingof titanium group elements in Group 4A of the Periodic Table, via anesterification reaction, wherein the above compound (1) is added to anesterification reaction tank for a final stage in a multi-stage reactionapparatus or to an esterification reaction product in a stage fortransportation to a melt polycondensation step.
 55. The process forproducing a polyester resin according to claim 53, wherein the compound(1) is added at such a stage as an esterification rate of anesterification reaction or ester exchange reaction product becomes atleast 90%.
 56. The process for producing a polyester resin according toclaim 53, wherein the compound (1) is added to an esterificationreaction product in a stage for transportation to a meltpolycondensation step.
 57. The process for producing a polyester resinaccording to claim 53, wherein the polycondensation is carried out inthe presence of (2) a compound of at least one member selected from thegroup consisting of metal elements of Group 1A of the Periodic Table,elements of Group 2A of the Periodic Table, manganese, iron and cobaltand (3) a phosphorus compound.
 58. The process for producing a polyesterresin according to claim 57, wherein a compound of at least one elementselected from the group consisting of metal elements of Group 1A of thePeriodic Table, elements of Group 2A of the Periodic Table, manganese,iron and cobalt is added to an esterification reaction tank for a finalstage in a multistage reaction apparatus.
 59. The process for producinga polyester resin according to claim 53, wherein the compound (1) is atitanium compound.
 60. A polyester resin produced by polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component, and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the periodic table, via anesterification reaction or an ester exchange reaction, wherein saidpolyester resin is produced via melt polycondensation and solid phasepolycondensation, and wherein wherein the intrinsic viscosity ([η₁]) ofthe melt polycondensation resin ranges from 0.35 to 0.75 dl/g as a valuemeasured at 30° C. in a solution in a mixed solvent ofphenol/tetrachloroethane (weight ratio: 1/1) and wherein the meltpolycondensation velocity (V₁) as a value obtained by dividing theintrinsic viscosity ([η₁]) of the resulting polyester resin by thereaction time, is at least 0.15 dl/g/hr, and wherein the intrinsicviscosity ([η₂]) of the solid phase polycondensation ranges from 0.70 to0.90 dl/g as a value measured at 30° C. in a solution in a mixed solventof phenol/tetrachloroethane (weight ratio: 1/1) and wherein the solidphase polycondensation velocity (V₂) as a value obtained by dividing thedifference ([η₂]-[η₁]) between the intrinsic viscosity ([η₂]) of theobtainable solid phase polycondensation resin and the intrinsicviscosity ([η₁]) of the melt polycondensation resin, by the reactiontime, ranges from 0.008 to 0.015 dl/g/hr.
 61. The polyester resinaccording to claim 60, wherein the temperature-rising crystallizationtemperature (Tc) of the resin in the molded product after the injectionmolding at 280° C., is from 150 to 180° C.
 62. The polyester resinaccording to claim 60, wherein the resin before the injection molding isone having an intrinsic viscosity ([η]) of from 0.70 to 0.90 dl/g and acolor coordinate value b of the Hunter's color difference formula of notmore than
 4. 63. The polyester resin according to claim 60, wherein thecontent of the compound (1) is from 0.002 to 1 mol as the total amount(T) of atoms of the compound (1) per 1 ton of the polyester resin. 64.The polyester resin according to claim 63, which is one polycondensed inthe coexistence of (2) a compound of at least one element selected fromthe group consisting of metal elements of Group Ia of the periodictable, elements of Group IIa of the periodic table, manganese, iron andcobalt, and (3) a phosphorus compound, wherein the content of thecompound (2) is from 0.04 to 5 mols as the total amount (M) of atoms ofthe compound (2) per 1 ton of the polyester resin, and the content ofthe compound (3) is from 0.02 to 4 mols as the total amount (P) of atomsof the compound (3) per 1 ton of the polyester resin.
 65. The polyesterresin according to claim 64, wherein the contents of the respectivecompounds (1), (2) and (3) are from 0.02 to 0.2 mol as the total amount(T) of atoms of the compound (1), from 0.04 to 0.6 mol as the totalamount (M) of atoms of the compound (2) and from 0.02 to 0.4 mol as thetotal amount (P) of atoms of the compound (3), per 1 ton of thepolyester resin, the acetaldehyde content (AA₁) is not more than 5.0ppm, the acetaldehyde content (AA₂) of the resin in a molded productafter injection-molded at 280° C. is not more than 20 ppm, and the hazeof a molded product with a thickness of 5 mm after the injection moldingat 280° C. is not more than 10%.
 66. The polyester resin according toclaim 60, wherein the compound (1) is a titanium compound, the compound(2) is a magnesium compound, and the compound (3) is a phosphoric acidester.
 67. The polyester resin according to claim 60, wherein, as adicarboxylic acid component, from 0.1 to 3 mol % of isophthalic acid orits ester-forming derivative based on the total dicarboxylic acidcomponent, and as a diol component, from 1 to 3 mol % of diethyleneglycol based on the total diol component, are copolymerized,respectively.
 68. A process for producing the polyester resin accordingto claim 60, which comprises polycondensing a dicarboxylic acidcomponent containing terephthalic acid or its ester-forming derivativeas the main component, and a diol component containing ethylene glycolas the main component in the presence of (1) a compound of at least onemember selected from the group consisting of titanium group elements inGroup 4A of the periodic table, (2) a compound of at least one elementselected from the group consisting of metal elements of Group Ia of theperiodic table, elements of Group IIa of the periodic table, manganese,iron and cobalt, and (3) a phosphorus compound, via an esterificationreaction or an ester exchange reaction, characterized in that theamounts of the respective compounds (1), (2) and (3) are such amountsthat their contents will be from 0.02 to 0.2 mol as the total amount (T)of atoms of the compound (1), from 0.04 to 0.6 mol as the total amount(M) of atoms of the compound (2) and from 0.02 to 0.4 mol as the totalamount (P) of atoms of the compound (3), per 1 ton of the polyesterresin.
 69. The process for producing a polyester resin according toclaim 68, wherein the ratio (P/T) of the total amount (P) of atoms ofthe compound (3) to the total amount (T) of atoms of the compound (1),is from 0.1 to
 10. 70. The process for producing a polyester resinaccording to claim 68, wherein the ratio (M/T) of the total amount (M)of atoms of the compound (2) to the total amount (T) of atoms of thecompound (1), is from 0.1 to
 10. 71. The process for producing apolyester resin according to claim 68, wherein the order for addition ofthe respective compounds (1), (2) and (3) to the reaction system is (3),then (2) and then (1).
 72. The process for producing a polyester resinaccording to claim 68, wherein the compound (1) is a titanium compound,the compound (2) is a magnesium compound, and the compound (3) is aphosphoric acid ester.
 73. The process for producing a polyester resinaccording to claim 72, wherein the titanium compound is added to thereaction system in the form of an ethylene glycol solution having atitanium atom concentration of from 0.01 to 0.3 wt % and a waterconcentration of from 0.1 to 1 wt %.
 74. The process for producing apolyester resin according to claim 68, wherein from 0.1 to 3 mol % ofisophthalic acid or its ester-forming derivative is used based on thetotal dicarboxylic acid component.
 75. A process for producing thepolyester resin of claim 60, which comprises polycondensing adicarboxylic acid component containing terephthalic acid or itsester-forming derivative as the main component and a diol componentcontaining ethylene glycol as the main component in the presence of (1)a compound of at least one member selected from the group consisting oftitanium group elements in Group 4A of the Periodic Table, via anesterification reaction or an ester exchange reaction, wherein the abovecompound (1) is added to an esterification reaction tank for a finalstage in a multi-stage reaction apparatus or to an esterificationreaction or ester exchange reaction product in a stage fortransportation to a melt polycondensation step.
 76. The process forproducing a polyester resin according to claim 75, which comprisespolycondensing terephthalic acid and ethylene glycol in the presence of(1) a compond of at least one member selected from the group consistingof titanium group elements in Group 4A of the Periodic Table, via anesterification reaction, wherein the above compound (1) is added to anesterification reaction tank for a final stage in a multi-stage reactionapparatus or to an esterification reaction product in a stage fortransportation to a melt polycondensation step.
 77. The process forproducing a polyester resin according to claim 75, wherein the compound(1) is added at such a stage as an esterification rate of anesterification reaction or ester exchange reaction product becomes atleast 90%.
 78. The process for producing a polyester resin according toclaim 75, wherein the compound (1) is added to an esterificationreaction product in a stage for transportation to a meltpolycondensation step.
 79. The process for producing a polyester resinaccording to claim 75, wherein the polycondensation is carried out inthe presence of (2) a compound of at least one member selected from thegroup consisting of metal elements of Group 1A of the Periodic Table,elements of Group 2A of the Periodic Table, manganese, iron and cobaltand (3) a phosphorus compound.
 80. The process for producing a polyesterresin according to claim 79, wherein a compound of at least one elementselected from the group consisting of metal elements of Group 1A of thePeriodic Table, elements of Group 2A of the Periodic Table, manganese,iron and cobalt is added to an esterification reaction tank for a finalstage in a multistage reaction apparatus.
 81. The process for producinga polyester resin according to claim 75, wherein the compound (1) is atitanium compound.
 82. The polyester resin according to claim 60,wherein the ratio (V₂/V₁) of this solid phase polycondensation velocityto the melt polycondensation velocity is within a range of from 0.04 to0.07.